Coordination number change of Ln(3+) ions in anhydrous alcoholic LnCl(3) solutions in the glassy state

Raman spectroscopic measurements were carried out for anhydrous alcoholic r are earth chloride solutions (LnCl(3). 20ROH; ROH = MeOH, EtOH, and n-PrOH) in the glassy state at liquid nitrogen temperature, Series behavior of the Ln-CI stretching Raman band is examined in conjunction with the formation of chloro complexes. The results are summarized as follows: (1) Comparing t he results with those in the liquid state at room temperature, more Cl- ion s tend to coordinate to heavy rare earth ions in the three alcohol solution s upon going from a liquid to a glassy state, while the coordination number of the Cl- ions of the light rare earth ions remains almost unchanged on v itrification. (2) In the former half region of the rare earth series, the c oordination number of the Cl- ions of the rare earth ions in the methanol L nCl(3) solution is apparently the same as that in the ethanol LnCl(3) solut ion. (3) In the latter half region, the higher chloro complexes, such as [L nCl(x+1) (ROH)(y - 2)]((z - 1)+) (x + y = 8; x = 1, z = 2 or x = 2, z = 1) are more abundant in the methanol LnCl(3) solution than in the ethanol and n-propanol LnCl(3) solutions.